This research is the first to assess directly Schwartz’s claim that the circular structure of values derives from value compatibilities or conflicts experienced in real-time behaviors. We differentiate two types of values: value traits guide perception and behavior over time and situations and value states guide real-time behavioral acts. We measured the value states of 374 participants for 13,873 behavioral acts with experience sampling, distinguishing volitional from non-volitional acts. As hypothesized, value states for volitional acts, but not for non-volitional acts reproduced the circular value structure. The importance hierarchies of value states differed substantially from the importance hierarchy of value traits, suggesting that the importance of value states depends more on situations than on the hierarchy of value traits.